Flame-hydrolytically produced titanium dioxide mixed oxide method of its production and its use

ABSTRACT

Flame-hydrolytically produced titanium dioxide mixed oxide having a BET surface of 10 to 150 m 2  /g and 1 to 30% by weight aluminum oxide or 1 to 30% by weight silicon dioxide is produced by evaporating aluminum chloride or silicon tetrachloride, transferring the evaporated aluminum chloride or silicon tetrachloride, together with an inert gas, into the mixing chamber of a burner, mixing them with hydrogen, air and gaseous titanium tetrachloride, burning the resulting 4-component mixture in the reaction chamber of the burner, and separating the titanium dioxide mixed oxide from the gaseous reaction products.

This is a division of application Ser. No. 08/139,708, filed Oct. 22,1993 now U.S. Pat. No. 5,451,390.

The present invention relates to a flame-hydrolytically producedtitanium dioxide mixed oxide, a method of its production and its use.

BACKGROUND OF THE INVENTION

It is known that titanium dioxide mixed oxide can be producedhydrolytically in the gaseous phase. Thus, published German PatentApplication DE-A 9 52 891 describes a method of producing mixed oxidesof aluminum and titanium or of titanium and silicon in which thetemperature is maintained in the range between 250° and 650° C.

Published German Patent Application DE-A 29 31 810 (U.S. Pat. No.4,297,143) describes a flame-hydrolytically produced silicondioxide--titanium dioxide mixed oxide containing 99.9 to 91.1% by weightsilicon dioxide and 0.1 to 9.9% by weight titanium dioxide.

Published German Patent Application DE-A 36 11 449 describes aflame-hydrolytically produced aluminum oxide--titanium oxide mixed oxidecontaining 56% by weight aluminum oxide and 44% by weight titaniumdioxide.

SUMMARY OF THE INVENTION

The present invention provides a flame-hydrolytically produced titaniumdioxide mixed oxide with a BET surface of 10 to 150 m² /g which contains1 to 30% by weight aluminum oxide or 1 to 30% by weight silicon dioxideas a component of the mixed oxide.

In a preferred embodiment of the invention, the titanium dioxide mixedoxide can have the following physicochemical properties:

    ______________________________________                                        Al.sub.2 O.sub.3 content                                                                            1-30                                                    (% by weight)                                                                 SiO.sub.2 content     1-30                                                    (% by weight)                                                                 Specific surface       10-150                                                 (m.sup.2 /g)                                                                  Primary (unagglomerated) particle size                                                               5-100                                                  (nm)                                                                          Stamping density (g/l)                                                                               50-400                                                 Annealing loss (2 hours at 1,000° C.)                                                        0.5-5                                                   (% by weight)                                                                 Chloride content      10 < 1                                                  (% by weight)                                                                 Rutile content (%)    20-90                                                   ______________________________________                                    

The invention also provides a method of producing a flame-hydrolyticallyproduced titanium dioxide mixed oxide in which anhydrous aluminumchloride or silicon tetrachloride is evaporated, transferred togetherwith an inert gas, e.g. nitrogen, into the mixing chamber of aconventional burner, mixed in the burner with hydrogen, air and gaseoustitanium tetrachloride in such proportions that the correspondinglycomposed desired Al₂ O₃ /TiO₂ mixed oxide or SiO₂ /TiO₂ mixed oxideresults, the 4-component mixture is burned in a reaction chamber, thenthe solid titanium oxide mixed oxide is separated from the gaseousreaction products and freed, if necessary, in moist air from adheringhydrogen chloride.

The flame-hydrolytic conversion of the invention can be carried out attemperatures of 1,000° to 3,000° C.

The titanium dioxide mixed oxide of the invention can be used for theproduction of catalysts, catalytic carriers, photocatalysts, ceramics,automobile paints and cosmetic articles (especially as UV absorbers insunscreen agents) and as heat stabilizers in silicone rubbers.

The titanium dioxide mixed oxide of the invention advantageously has arather high temperature resistance of the surface. It is fine, veryhomogenous, very pure and highly dispersible.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The invention is illustrated by the following examples:

EXAMPLES

AlCl₃ and TiCl₄ or SiCl₄ and TiCl₄ are volatilized in two separateevaporators (evaporator temperatures: AlCl₃ 250° C., SiCl₄ 100° C.,TiCl₄ 200° C.) and the chloride vapors conducted by means of nitrogeninto the mixing chamber of a burner. There, they are mixed with hydrogenand dried air and/or oxygen and burned in a reaction chamber. Thereaction products are cooled in the coagulation zone to approximately110° C. The mixed oxides are subsequently separated with a filter.Adhering chloride is removed by treating the powder with moist air at atemperature between 500° and 700° C.

Tables 1 and 2 list the reaction conditions and the product propertiesfor various mixed oxides.

Temperature resistance of the specific surface

The specific surface of mixed oxides 4 and 9 was determined, by way ofexample, after calcination at temperatures between 500° and 800° C. Theresidence time was 4 hours in each instance. Undoped pyrogenic titaniumoxide P 25 (BET 50 m² /g) was used as reference material. The resultsare shown in FIG. 1.

The specific surface of P 25 breaks in sharply after 600° C.

The doping with aluminum oxide yields a material with a distinctly morestable surface (800° C.: 30 m² /g instead of 12 m² /g in the case of P25).

The addition of silicon dioxide yields a powder whose surface is stableover the tested temperature range.

The novel materials can be used at high temperatures and are thereforeespecially suitable for the production of catalysts and catalyticcarriers.

                                      TABLE 1                                     __________________________________________________________________________    Al.sub.2 O.sub.3 /TiO.sub.2 mixed oxides                                                             Stamping                                                                           Annealing                                                                          Chloride                                        TiCl.sub.4                                                                       AlCl.sub.3                                                                       H.sub.2                                                                          Air                                                                              Al.sub.2 O.sub.3                                                                  BET Density                                                                            loss content                                      No.                                                                              (g/h)                                                                            (g/h)                                                                            (l/h)                                                                            (l/h)                                                                            (%) (m.sup.2 /g)                                                                      (g/l)                                                                              (%)  (%)                                          __________________________________________________________________________    1   264                                                                              19                                                                              236                                                                              1643                                                                             6.1 98  159  1.6  0.06                                         2   236                                                                              50                                                                              236                                                                              1643                                                                             16.2                                                                              103 145  1.7  0.15                                         3  1466                                                                             114                                                                              448                                                                              1276                                                                             6.6 56  308  1.1  0.10                                         4  1363                                                                             188                                                                              448                                                                              1274                                                                             11.2                                                                              47  329  0.7  0.16                                         5  1292                                                                             285                                                                              448                                                                              1276                                                                             16.7                                                                              58  272  1.0  0.15                                         __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________    SiO.sub.2 /TiO.sub.2 mixed oxides                                                                    Stamping                                                                           Annealing                                                                          Chloride                                        TiCl.sub.4                                                                       SiCl.sub.4                                                                       H.sub.2                                                                          Air                                                                              SiO.sub.2                                                                         BET Density                                                                            loss content                                      No.                                                                              (g/h)                                                                            (g/h)                                                                            (l/h)                                                                            (l/h)                                                                            (%) (m.sup.2 /g)                                                                      (g/l)                                                                              (%)  (%)                                          __________________________________________________________________________    6   268                                                                              17                                                                              236                                                                              1643                                                                             5.0 105 162  1.1  0.02                                         7   231                                                                              54                                                                              236                                                                              1643                                                                             16.5                                                                              112 151  0.9  0.02                                         8  1423                                                                             118                                                                              448                                                                              1276                                                                             6.5 47  287  1.3  0.13                                         9  1346                                                                             208                                                                              448                                                                              1276                                                                             9.5 49  274  1.0  0.09                                         10 1258                                                                             296                                                                              448                                                                              1276                                                                             16.5                                                                              48  258  1.2  0.06                                         __________________________________________________________________________

BRIEF DESCRIPTION OF FIGURES OF DRAWING

In the drawings,

FIG. 1 is a graph showing the Temperature Stability of the specificsurface; and

FIG. 2 is a schematic view of a burner which can be used to carry outthe process of the present invention.

In carrying out the invention in the apparatus shown in FIG. 2, thegas-forming metal chlorides, i.e., titanium tetrachloride and aluminumchloride or silicon tetrachloride, are introduced with an inert gasthrough the inlets 4 and 5 into the mixing chamber 8. Hydrogen and driedair are preheated and introduced through the inlets 6 and 7 into themixing chamber 8. The four component mixture is advanced into thecombustion chamber 1 of the burner and burned in a flame. In order tosustain the flame, an additional quantity of hydrogen can be suppliedthrough the annular chamber 2 which surrounds the combustion chamber 1.

What is claimed is:
 1. A member of the group consisting of catalysts,catalytic carriers, photocatalysts, automobile paints, cosmetic articlesand silicone rubbers comprising a flame-hydrolytically produced titaniumdioxide mixed oxide having a BET surface of 10 to 150 m² /g whichcontains 1-30% by weight of a member of the group consisting of aluminumoxide and silicon dioxide as a component of the mixed oxide, and abalance of the titanium dioxide and unavoidable impurities.
 2. Asilicone rubber comprising a flame-hydrolytically produced titaniumdioxide mixed oxide as a heat stabilizer, having a BET surface of 10 to150 m² /g which contains 1 to 30% by weight of a member of the groupconsisting of aluminum oxide and silicon dioxide as a component of themixed oxide, and a balance of the titanium dioxide and unavoidableimpurities.
 3. The flame-hydrolytically produced titanium dioxide mixedoxide of claim 1, having a primary unagglomerated particle size of 5-100nm.
 4. The flame-hydrolytically produced titanium dioxide mixed oxide ofclaim 1, having a stamping density of 50-400 g/l.
 5. Theflame-hydrolytically produced titanium dioxide mixed oxide of claim 1,having an annealing loss over two hours at 1,000° C. of 0.5-5% byweight.
 6. The flame-hydrolytically produced titanium dioxide mixedoxide of claim 1, wherein the chloride content is less than 1% byweight.
 7. The flame-hydrolytically produced titanium dioxide mixedoxide of claim 1, wherein the rutile content is 20-90%.